EP0463740B1 - Schutzschichten - Google Patents
Schutzschichten Download PDFInfo
- Publication number
- EP0463740B1 EP0463740B1 EP91304855A EP91304855A EP0463740B1 EP 0463740 B1 EP0463740 B1 EP 0463740B1 EP 91304855 A EP91304855 A EP 91304855A EP 91304855 A EP91304855 A EP 91304855A EP 0463740 B1 EP0463740 B1 EP 0463740B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- barrier
- lamellae
- atomic oxygen
- formaldehyde
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000004888 barrier function Effects 0.000 title claims description 40
- 230000001681 protective effect Effects 0.000 title claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 229910052902 vermiculite Inorganic materials 0.000 claims description 27
- 239000010455 vermiculite Substances 0.000 claims description 27
- 235000019354 vermiculite Nutrition 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 19
- 239000011707 mineral Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 230000001427 coherent effect Effects 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 description 8
- 229940094522 laponite Drugs 0.000 description 7
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 7
- 101100379068 Caenorhabditis elegans apc-2 gene Proteins 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920001646 UPILEX Polymers 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010427 ball clay Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31859—Next to an aldehyde or ketone condensation product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31859—Next to an aldehyde or ketone condensation product
- Y10T428/31862—Melamine-aldehyde
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31924—Including polyene monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31931—Polyene monomer-containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
Definitions
- the invention relates to protective barriers and to components protected thereby.
- the present invention relates to, and is concerned with, the use of layer minerals which exhibit barrier properties against atomic oxygen.
- an aerospace vehicle comprises external surfaces susceptible to atomic oxygen attack which have a protective barrier against such attack, said barrier comprising a substantially continuous layer of lamellae of a film-forming, 2:1 phyllosilicate layer mineral which exhibit barrier properties against atomic oxygen.
- an aerospace vehicle component comprises external surfaces susceptible to atomic oxygen attack which have a protective barrier against such attack, said barrier comprising a substantially continuous layer of lamellae of a film-forming, 2:1 phyllosilicate layer mineral which exhibits barrier properties against atomic oxygen.
- the invention is directed to the use as a protective barrier against atomic oxygen attack of lamellae of a film-forming, 2:1 phyllosilicate layer mineral which exhibit barrier properties against atomic oxygen.
- lamellae as used in this specification means tiny particles of the layer mineral obtained by subjecting the mineral to a chemical delaminating process to form an aqueous colloidal dispersion of high aspect ratio particles or platelets of the mineral from which a film can be formed.
- the lamellae have a thickness of less than 0.5»m, usually less than 0.05»m and preferably of the order of or less than 0.005»m and an aspect ratio (ie length or breadth divided by thickness) of at least 10, preferably at least 100 and up to 1000 or more, eg 10000.
- the layer mineral is selected from the group consisting of smectites, preferably hectorite and montmorillonite, and vermiculite.
- vermiculite as used in this specification means all materials known mineralogically and commercially as vermiculite including chlorite-vermiculites.
- barriers having surprising and significant protective barrier properties against atomic oxygen comprise a substantially continuous layer of lamellae at very low thicknesses, eg as low as 0.025»m, but preferably the minimum thickness of the layer is at least 0.1»m, preferably at least 0.3»m, and particularly up to 1»m.
- the layer mineral is vermiculite.
- the barrier preferably comprises, particularly when the layer mineral is vermiculite, at least one component selected from a binder and a polymeric anchor coating interposable between the lamellae and the substrate or surface.
- the binder is an organic binder and may be any film-forming polymeric or oligomeric species or precursor therefor that assists in forming a film of the lamellae of the layer mineral and does not disrupt the film-forming capability thereof.
- the polymeric binder is selected from functionalised polyolefins, especially maleimised polybutadiene, and a liquid formaldehyde resin such as urea formaldehyde, melamine formaldehyde, phenol formaldehyde, resorcinol formaldehyde, cresol formaldehyde or mixtures thereof, especially melamine formaldehyde.
- the binder when present, comprises at least 5% by weight of the layer and, more particularly, between 10% and 50%, and especially between 15% and 35%, by weight of the layer.
- the polymeric anchor coating comprises a styrene/acrylamide copolymer of the type more particularly described in GB-A-1174328 and GB-A-1134876.
- the anchor coating when present, is less than 1»m thick and, more particularly, is less than 0.5»m, especially less than 0.25»m, thick.
- the protective barrier is formed by applying the lamellae as a slurry or dispersion and removing the dispersion medium to form a coherent layer.
- the dispersion medium comprises water and the slurry or dispersion comprises between 0.5% and 20%, more especially between 1% and 10%, by weight of lamellae.
- the substrate to which the protective barrier is applied in accordance with the invention is conveniently selected from structural parts of aerospace vehicles which have surfaces which are exposed to atomic oxygen environments in use or to components thereof exposed to those environments in use, the components being for example solar panels (the barriers being relatively flexible and transparent over a wide range of electromagnetic frequencies) and antennae.
- the substrate may also be a polymeric film.
- the polymeric film is selected from aromatic polyesters and aromatic polymers comprising divalent aromatic units containing divalent connecting groups selected from ketone, sulphone, sulphoxide or imide, the units being connected by ether and/or thioether linkages.
- a free-standing film of vermiculite lamellae was prepared by forming a wet film of lamellae of vermiculite slurry GP-903 available from W R Grace & Co and allowing the film to dry in air.
- the wet film was formed on a glass substrate using a 2% by weight aqueous slurry of the lamellae.
- the resultant film was 30»m thick.
- Samples of the film were subjected to a simulated atomic oxygen regime using a research plasma reactor available from Polar Materials Inc, USA, the samples being located on a 127mm diameter powered aluminium electrode spaced 44.5mm from a 114mm copper electrode. Parts of the samples were masked using a small silicon wafer on the surface of the sample to enable etch depths to be analysed using an ⁇ -step analyser available from Tencor, USA.
- vermiculite lamellae film samples exhibited a weight loss following removal from the reactor after treatment, allowing the samples to equilibrate in ambient atmosphere caused the sample weights to return to the untreated values. Furthermore, using the ⁇ -step analyser, no measurable step could be discerned on the material surface. Scanning electron micrographs of the untreated and treated samples showed no discernible differences.
- vermiculite lamellae film appeared to be unaffected by the simulated atomic oxygen environment to which it had been subjected.
- the polymers show little resistance to the simulated atomic oxygen environment.
- Samples of a polymer composite of Victrex PEEK and carbon fibres available from ICI under the trade name APC-2 were subjected to the simulated atomic oxygen environment described in Example 1 following degassing for 1 hour.
- the samples tested were approximately 3mm thick and had a surface area of about 10 ⁇ 3m ⁇ 2.
- the samples were coated with lamellae of vermiculite slurry GP-903, available from W R Grace & Co, USA (using a 6.5% by weight slurry which included about 20% by weight of maleinised polybutadiene as a binder), and a synthetic hectorite available from Laporte Industries Limited under the trade name Laponite B (using a 2% by weight slurry).
- the 0.3»m vermiculite coating was achieved using a number 2 Meyer bar and the Laponite B and the thicker vermiculite coatings were achieved using a number 4 Meyer bar.
- virgin APC-2 composite material and APC-2 composite material having an aluminium coating deposited thereon by electron beam evaporation were also subjected to the simulated atomic oxygen environment described in Example 1. The results are summarised in Table 2.
- Samples of APC-2 were coated with lamellae of vermiculite and Laponite B slurries as described in Example 3. Meyer bars numbers 2 and 4 were used for the vermiculite and the Laponite B, respectively.
- the slurry contained 6.5% by weight of the lamellae and varying amounts of the polymeric binders maleimised polybutadiene (MPBD) or melamine formaldehyde resin (MF).
- One sample (marked * in Table 3 below) was pre-coated with a polymeric anchor coat of a styrene/ 2-ethyl hexyl acrylate/methacrylic acid/N-butoxymethyl acrylamide copolymer of the type described in the aforementioned GB-A-1174328 and GB-A-1134876.
- the coating was applied using a number 1 Meyer bar as a 3% by weight solution in isopropyl alcohol and containing sulphuric acid as catalyst and dried in air at ambient temperature to give a dry coating of thickness 0.12»m.
- the coated samples were then subjected to an adhesion test.
- the samples were cross-scored on their coated side to give a plurality of rectangles of substantially equal area.
- An adhesive tape was then applied to the scored coating and the area of coating remaining adhered to the substrate was determined and is quoted as a percentage in Table 3 below.
- a sample was made similar to that marked * in Table 3 above and it was subjected to thermal cycling from liquid nitrogen temperature to 90°C. The adhesion of the vermiculite coating to the APC-2 substrate appeared to improve.
- samples of ICI development composites designated APC (HTA) (the polymeric matrix being a polyethersulphone and APC (ITX) (the polymeric matrix being a polyetherketone).
- HTA the polymeric matrix being a polyethersulphone
- APC the polymeric matrix being a polyetherketone
- the samples were coated with lamellae of vermiculite slurries GP-903 using a 6.5% by weight slurry which included about 20% by weight of MPBD as binder and with Laponite B using a 2% by weight slurry.
- the 0.3»m vermiculite coating was achieved using a number 2 Meyer bar and the Laponite B and the thicker vermiculite coatings were achieved using a number 4 Meyer bar.
- Table 4 The results are summarised in Table 4.
- Example 6 The procedure of Example 6 was repeated for further samples and the coatings and results are summarised in Table 5. The samples were equilibriated for 14 days before the mass loss figures were determined. Vermiculite slurry GP-923 is also available from W R Grace & Co. Sumecton (trade name) is a synthetic hectorite available from Kunimine Industries, Japan.
- a 1-2»m layer of Laponite S lamellae was formed on a silica substrate and the absorbance of radiation in the visible and UV regions was determined for it.
- the sample had a low absorbance, ie it was substantially transparent to the radiation, in both the visible and UV regions.
- Subtrates precoated with an anchor coat as described in Example 4, were coated with bentonite which was applied as 7.5% by weight aqueoue slurry which included 35% by weight of MF as binder using Meyer bars numbers 2 and 6 to achieve dry coating thicknesses of 0.3»m and 1.7»m, respectively. Both samples were degassed for 1 hour and subjected to the simulated atomic oxygen environment described in Example 1. Even without equilibriation, both samples exhibited good barrier properties, ie ⁇ 100»g/cm2 weight loss.
- Polymeric films were assessed in the reactor as described in Example 1 both without a protective coating and with a protective coating, the films assessed being:-
- the samples were mounted in a ring having an inwardly-extending flange which protected the periphery of the film.
- the samples were degassed for 1 hour and the quoted mass losses of the samples were determined after a 5 day equilibrium period.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Road Signs Or Road Markings (AREA)
Claims (15)
- Raumfahrtfahrzeug, das äußere Oberflächen umfaßt, die anfällig gegen einen atomaren Sauerstoffangriff sind, das eine Schutzbarriere gegen einen derartigen Angriff hat, wobei diese Barriere eine im wesentliche kontinuierliche Schicht von Lamellen eines filmbildenden, 2:1 Phyllosilicatschichtmineral ist, das Barriere-Eigenschaften gegen atomaren Sauerstoff zeigt.
- Raumfahrtfahrzeugkomponente, das äußere Oberflächen umfaßt, die anfällig gegen einen atomaren Sauerstoffangriff sind, das eine Schutzbarriere gegen einen derartigen Angriff hat, wobei diese Schicht eine im wesentliche kontinuierliche Schicht von Lamellen eines filmbildenden, 2:1 Phyllosilicatschichtminerals ist, das Barriere-Eigenschaften gegen atomaren Sauerstoff zeigt.
- Verwendung der Lamellen eines filmbildenden, 2:1 Pyllosilicatschichtminerals, das Barriere-Eigenschaften gegen atomaren Sauerstoff zeigt als Schutzbarriere gegen einen Angriff atomaren Sauerstoffs.
- In der Erfindung, wie in jedem der vorangehenden Ansprüche definiert, umfaßt diese Barriere zumindest eine Komponente, die aus einem polmeren Bindemittel und einer polymeren Haftschicht ausgewählt wird, die zwischen die Lamellen und das Substrat oder die Oberfläche dazwischen angeordnet werden kannn.
- In der Erfindung, wie in Anspruch 4 definiert, umfaßt das polymere Bindemittel ein funktionalisiertes Polyolefin, insbesondere maleimisiertes Polybutadien und ein flüssiges Formaldehydharz, wie Harnstofformaldehyd, Melaminformaldehyd, Phenolformaldehyd, Resorcinformaldehyd, Kresolformaldehyd oder Mischungen davon, insbesondere Melaminformaldehyd.
- Schutzbarriere auf einem Substrat zum Schutz der Oberfläche darauf gegen einen atomaren Sauerstoffangriff, wobei diese Barriere eine im wesentlich kontinuierliche Schicht von Lamellen eines filmbildenden, 2:1 Phyllosilicatschichtminerals ist, das Barriere-Eigenschaften gegen atomaren Sauerstoff in einem polymeren Bindemittel zeigt, wobei dieses Bindemittel ein funktionalisiertes Polyolefin, insbesondere maleimisiertes Polybutadien und ein flüssiges Formaldehydharz, wie Harnstofformaldehyd, Melaminformaldehyd, Phenolformaldehyd, Resorcinformaldehyd, Kresolformaldehyd oder Mischungen davon, insbesondere Melaminformaldehyd umfaßt.
- In der Erfindung, wie in jedem einzelnen der Ansprüche 4 bis 6 definiert, umfaßt das Bindemittel, falls vorhanden, zumindest 5 Gew.% der Schicht und bevorzugter zwischen 10 Gew.% und 30 Gew.% und insbesondere zwischen 15 Gew.% und 25 Gew.% der Schicht.
- Schutzbarriere auf einem Substrat zum Schutz einer Oberfläche darauf gegen atomaren Sauerstoffangriff, wobei diese Barriere eine im wesentliche kontinuierliche Schicht von Lamellen eines filmbildenden, 2:1 Phyllosilicatschichtminerals, das Barriere-Eigenschaften gegen atomaren Sauerstoff zeigt und eine polymere Haftschicht, die zwischen die Barriere und dieses Substrat dazwischen angeordnet werden kann, umfaßt.
- In der Erfindung, wie in jedem einzelnen der Ansprüche 4 bis 8 definiert, umfaßt die polymere Haftschicht, falls vorhanden, ein Styrol/Acrylamid Copolymer und besonders bevorzugt ein Styrol/2-Ethylhexylacrylat/Methacrylsäure/N-Butoxymethylacrylamid Copolymer.
- In der Erfindung, wie in jedem einzelnen der Ansprüche 4 bis 9 definiert, ist die Haftschicht, falls vorhanden, weniger als 1 »m dick und besonders bevorzugt weniger als 0,5 »m, insbesondere weniger als 0,25 »m dick.
- In der Erfindung, wie in jedem einzelnen der vorangehenden Ansprüchen definiert, wird das Schichtmineral aus der Gruppe, die aus Smectiten, bevorzugt Hectorit und Montmorillonit und Vermiculit besteht, ausgewählt.
- In der Erfindung, wie in jedem einzelnen der vorangehenden Ansprüchen definiert, umfaßt diese Barriere im wesentlichen eine kontinuierliche Schicht von Lamellen von zumindestens 0,1 »m, bevorzugt zumindest 0,3 »m dick und insbesondere bis zu 1 »m dick.
- In der Erfindung, wie in jedem einzelnen der vorangehenden Ansprüche definiert, ist das Schichtmineral Vermiculit.
- In der Erfindung, wie in jedem einzelnen der vorangehenden Ansprüche definiert, wird die Schutzbarriere gebildet, indem die Lamellen als wäßrige Aufschlämmung oder Dispersion aufgebracht werden und das Wasser entfernt wird, um eine kohärente Schicht zu bilden.
- In der Erfindung, wie in Anspruch 14 definiert, enthält die Aufschlämmung oder Dispersion zwischen 0,5% und 20%, besonders bevorzugt zwischen 1% und 10% des Gewichts an Lamellen.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9013702 | 1990-06-20 | ||
GB909013702A GB9013702D0 (en) | 1990-06-20 | 1990-06-20 | Protective barriers |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0463740A1 EP0463740A1 (de) | 1992-01-02 |
EP0463740B1 true EP0463740B1 (de) | 1995-12-06 |
Family
ID=10677883
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91304855A Expired - Lifetime EP0463740B1 (de) | 1990-06-20 | 1991-05-29 | Schutzschichten |
Country Status (7)
Country | Link |
---|---|
US (1) | US5234761A (de) |
EP (1) | EP0463740B1 (de) |
JP (1) | JP2997093B2 (de) |
CA (1) | CA2044218A1 (de) |
DE (1) | DE69115136T2 (de) |
ES (1) | ES2080250T3 (de) |
GB (1) | GB9013702D0 (de) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9102374D0 (en) * | 1991-02-04 | 1991-03-20 | Ici Plc | Polymeric film |
GB9112827D0 (en) * | 1991-06-14 | 1991-07-31 | Ici Plc | Polymeric film |
GB9112843D0 (en) * | 1991-06-14 | 1991-07-31 | Ici Plc | Polymeric film |
US5312685A (en) * | 1992-07-06 | 1994-05-17 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Atomic oxygen protective coating with resistance to undercutting at defect sites |
US6361876B1 (en) * | 1992-08-10 | 2002-03-26 | Mcdonnell Douglas Corporation | Durable protected optical coatings |
EP0627495B1 (de) * | 1993-05-10 | 1998-08-12 | Optical Coating Laboratory, Inc. | Selbstheilende UV-undurchlässige Beschichtung mit flexiblem Polymersubstrat |
EP0666612B1 (de) * | 1994-02-04 | 2001-10-24 | Orbital Sciences Corporation | Sich selbst entfaltende Wendelstruktur |
US5668565A (en) * | 1994-12-22 | 1997-09-16 | Orbital Science Corporation | Flexible feed line for an antenna system |
US6087016A (en) * | 1997-06-09 | 2000-07-11 | Inmat, Llc | Barrier coating of an elastomer and a dispersed layered filler in a liquid carrier |
US6232389B1 (en) | 1997-06-09 | 2001-05-15 | Inmat, Llc | Barrier coating of an elastomer and a dispersed layered filler in a liquid carrier and coated articles |
AU7837198A (en) * | 1997-06-09 | 1998-12-30 | Herberts G.M.B.H. | Aqueous coating composition of a polymer and exfoliated platelet filler |
US7303797B1 (en) * | 1999-02-16 | 2007-12-04 | E.I. Du Pont De Nemours And Company | Gas barrier coating system for polymeric films and rigid containers |
CN105151324A (zh) * | 2015-09-22 | 2015-12-16 | 上海卫星工程研究所 | 天基成像雷达卫星原子氧遮蔽装置及其使用方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5320959B2 (de) * | 1973-05-14 | 1978-06-29 | ||
US4174358A (en) * | 1975-05-23 | 1979-11-13 | E. I. Du Pont De Nemours And Company | Tough thermoplastic nylon compositions |
EP0044160B1 (de) * | 1980-07-11 | 1986-09-17 | Imperial Chemical Industries Plc | Faserige Verbundstoffe sowie deren Herstellung und Verwendung |
EP0075396B1 (de) * | 1981-09-14 | 1985-06-05 | Imperial Chemical Industries Plc | Wässrige Überzugsmittel |
US4664980A (en) * | 1984-09-14 | 1987-05-12 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Oxidation protection coatings for polymers |
US4800041A (en) * | 1985-11-04 | 1989-01-24 | Armstrong World Industries, Inc. | Suspensions of sheet silicate materials and products made therefrom |
US4980206A (en) * | 1986-09-15 | 1990-12-25 | The Boeing Company | Method for improving atomic oxygen resistance |
DE3707388A1 (de) * | 1987-03-07 | 1988-09-15 | Basf Lacke & Farben | Waessrige schichtsilikatdispersionen, verwendung dieser dispersionen als lackhilfsmittel und wasserverduennbare, schichtsilikate enthaltende beschichtungszusammensetzungen |
DE3823967A1 (de) * | 1988-07-15 | 1990-01-18 | Heinz B Mader | Plattenfoermiges, ebenes oder gewoelbtes bauelement in sandwichbauweise, insbesondere zur verwendung in luftfahrzeugen |
-
1990
- 1990-06-20 GB GB909013702A patent/GB9013702D0/en active Pending
- 1990-07-31 US US07/559,953 patent/US5234761A/en not_active Expired - Lifetime
-
1991
- 1991-05-29 ES ES91304855T patent/ES2080250T3/es not_active Expired - Lifetime
- 1991-05-29 EP EP91304855A patent/EP0463740B1/de not_active Expired - Lifetime
- 1991-05-29 DE DE69115136T patent/DE69115136T2/de not_active Expired - Fee Related
- 1991-06-10 CA CA002044218A patent/CA2044218A1/en not_active Abandoned
- 1991-06-18 JP JP3145699A patent/JP2997093B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2997093B2 (ja) | 2000-01-11 |
ES2080250T3 (es) | 1996-02-01 |
EP0463740A1 (de) | 1992-01-02 |
DE69115136D1 (de) | 1996-01-18 |
JPH04250035A (ja) | 1992-09-04 |
US5234761A (en) | 1993-08-10 |
DE69115136T2 (de) | 1996-06-05 |
GB9013702D0 (en) | 1990-08-08 |
CA2044218A1 (en) | 1991-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0463740B1 (de) | Schutzschichten | |
Schmidt et al. | Epoxy adhesion to metals | |
US5780163A (en) | Multilayer coating for microelectronic devices | |
KR100745852B1 (ko) | 미세균열 저항성이 개선된 적층 제품 및 그의 제조방법 | |
US5609925A (en) | Curing hydrogen silsesquioxane resin with an electron beam | |
EP0659904B1 (de) | Verdampftes Hydrogensilsesquioxan zum Anscheiden eines Überzugs | |
EP0900250B2 (de) | Schutzbeschichtungen aus lithium- und kaliumkopolysilikates | |
US5753374A (en) | Protective electronic coating | |
AU2003284639A1 (en) | Gas barrier multilayer film | |
EP1373388B1 (de) | Trennfilme | |
US4791008A (en) | Coating compositions and method for improving the properties of coated substrates | |
Kayhan et al. | Evaluation of two new white silicone thermal control paints under atomic oxygen | |
US5629066A (en) | Resin article having anti-static property | |
Marinkovic et al. | Preparation and properties of sputtered “glassy” carbon films | |
US6004680A (en) | Method of coating pre-primed polyolefin films | |
Konstadinidis et al. | X-ray photoelectron study of chemical interactions at Ti/polymer interfaces | |
Yoshiaki et al. | Wettability control of polystyrene by ion implantation | |
US5569493A (en) | Preparation of cured cyanate ester resins and composites for metal plating | |
EP0832945B1 (de) | Zusammensetzung für Überzugsmittel und Verbundfilm | |
Pola et al. | Polymer-stabilized nano-sized tellurium films by laser-induced chemical vapour co-deposition process | |
Watanabe | Aluminium nitride thin films prepared by ion beam assisted deposition method | |
Jeong et al. | Reaction mechanism between BN‐sprayed graphite and molten Al in vacuum, and its application to the evaporation source for reactive metals including Al | |
Nakamae et al. | Characterization of the interface between a cured epoxy resin and aluminum | |
Ruckman et al. | Ion and electron beam processing of condensed molecular solids to form thin films | |
Shi et al. | Ion-beam induced modifications of Sb Al bilayers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE ES FR GB IT |
|
17P | Request for examination filed |
Effective date: 19920527 |
|
17Q | First examination report despatched |
Effective date: 19931001 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE ES FR GB IT |
|
REF | Corresponds to: |
Ref document number: 69115136 Country of ref document: DE Date of ref document: 19960118 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2080250 Country of ref document: ES Kind code of ref document: T3 |
|
ITF | It: translation for a ep patent filed | ||
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20020508 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20020522 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20020529 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20020610 Year of fee payment: 12 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030529 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030530 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20031202 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20030529 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040130 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030530 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050529 |